The present invention relates to 2,4,4-trisubstituted tetrahydro pyranyl esters defined according to the structure: ##STR2## wherein R.sub.1 represents methyl or ethyl and R.sub.2 represents C.sub.2 -C.sub.4 straight chain or branched chain alkyl or alkenyl and uses thereof in order to alter, modify or enhance the aroma of consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
A fruity, citrusy, grapefruit, green, herbaceous, chamomile, floral, lily, rose, muguet, live flower petal-like, sauge sclaree, tobacco, mentha citrata, lavender, witch hazel, woody, orris, earthy, early morning forest path, oolong tea, ozoney, natural waxey, piney, guiacwood-like, sweet, jasmine and geranium aromas with chamomile, woody, soft woody, cabreuva, sauge sclaree, lavender, winey, floral, rose, copaiba oil-like, geranium, earthy, early morning forest path, fatty, oatmeal, herbaceous, spicy and black pepper undertones are highly desirable in several types of perfume compositions, perfumed articles and colognes.
The perfume use of 2,4,4-trisubstituted tetrahydro pyranols having the structures: ##STR3## is disclosed in the literature as follows:
(a) the perfume use of the compound having the structure: ##STR4## USSR Pat. No. 620487 of July 17, 1978 (Chemical Abstracts 89:185929p);
(b) the compound having the structure: ##STR5## USSR Pat. No. 638597 of Dec. 28, 1978 (Chemical Abstracts, Volume 90:109812a);
(c) the compound having the structure: ##STR6## USSR Pat. No. 618374 of Aug. 5, 1978 (Chemical Abstracts 89:179861u); tetrahydro pyranyl esters are also known for their use in perfumery, specifically:
(a) the compound having the structure: ##STR7## disclosed by Arctander "Perfume And Flavor Chemicals (Aroma Chemicals)", Volumes I and II, at Monograph 2926 as follows: ##STR8##
(b) the compound having the structure: ##STR9## disclosed by Arctander, at Monograph 1935, to wit: ##STR10##
The 2,4,4-trisubstituted tetrahydro pyranyl esters of our invention are novel compounds and have unexpected, unobvious and advantageous organoleptic properties with respect to the organoleptic properties of the compounds of the prior art.
Furthermore, considerable difficulties have heretofore been encountered in using compounded hypochlorite bleach orsterilizigsolutions with perfumed oils so that a stable long-lasting, single phase commercially feasible bleach or sterilizing solution has been difficult to obtain, particularly wherein the desired aroma of the article bleached or sterilized (e.g., clothing) has a pleasant and stable and consistent aroma on drying (and not the usual "hypochlorite-bleached-article" aroma). The problem has been defined in United Kingdom Patent Specification No. 886,084 published on Jan. 3, 1962 wherein it is stated that a stable "dispersion" of hypochorite-resistent perfume in aqueous solutions of hypochlorites was formulated. United Kingdom Patent Specification No. 886,084 discloses the preparation of an aqueous "solution" of a hypochlorite containing a hypochlorite resistant perfume and a surface active quaternary ammonium compound of the betaine type soluble in the hypochlorite solution. Such ammonium compounds have the generic structure: ##STR11## wherein each of R.sub.1 ", R.sub.2 ", R.sub.3 " and R.sub.4 " are alkyl. One of the features of the perfumed solutions produced in accordance with said United Kingdom Patent Specification No. 886,084 is indicated to be that the solution exhibits foaming properties. Another feature of United Kingdom Patent Specification No. 886,084 is stated to be that the perfumed solutions covered by the patent are found to be clear and homogeneous after eight weeks of storage at room temperature. Nevertheless, betaines such as "Ambiteric D" as are discussed therein are not so broadly useful when used in concentrations of from 0.15% up to 4.0% (based on total weight of bleach or sterilizing solution) as to have the ability to be used in conjunction with perfume oils which should be incorporated into thickened, high viscous hypochlorite bleaches or sterilizers having excellent surface tension properties so that long lasting stable soluble single phase thickened perfumed aqueous alkali metal hypochlorite bleach or sterilizing solutions having long lasting pleasing stable aromas are obtained, particularly where the quantity of perfume oil in the bleach or sterilizing substance is at levels of between 0.02% and 0.8% by weight of the total bleach or sterilizing solution. The need for such aromas (e.g., "citrusy") to be present in such bleach or sterilizing solutions exists so that the disagreeable characteristic "hypochorite" aroma is substantially eliminated from aromas of the product to which the bleach or sterilizing solution is applied; particularly on dry-out, as well as from the aroma of the hands of the user when they are in direct contact with such bleach or sterilizing solutions.
U.S. Pat. Nos. 3,560,389 also discloses the feasibility of using perfume oils in hypochlorite bleaches or sterilizers at column 3, lines 37-40 but the disclosure is limited to inclusion of various detergents in addition to amine oxides, such as lithium lauryl sulfate and sodium lauryl ether sulfate and/or is further limited to include hydrotropes such as sodium xylene sulfonate in addition to the amine oxide. Exclusion of such hydrotropes and detergents additional to the 2,4,4-trisubstituted tetrahydropyranol esters of our invention is desirable not only to cause 2,4,4-trisubstituted tetra-hydro pyranyl esters of our invention to function properly, but also from an ecological standpoint.
European Chemical News, Volume 13, Jan. 18, 1968, sets forth a stbiosus of South African Pat. No. 67/4667 which corresponds to U.S. Pat. No. 3,560,389, but the reference also states at page 42:
"Alternatively, a detergent with bleaching or bacteriocidal properties can be formulated. Perfuming bleaching solutions is now possible." PA0 "Claim: An aromatic liquid bleaching composition containing, as active ingredient, sodium hypochlorite, which comprises one or more of simple perfumes or compounded perfumes selected from the group consisting of anisole, benzophenone, benzylphenyl ether, bromelia, cedrenyl acetate, p-tertiary butylcyclohexanol, dimethylbenzylcarbinyl acetate, dihydroterpinyl acetate, diphenyl oxide, dimethylbenzylcarbinol, dimethylphenylcarbinol, dihydroterpineol, fenchyl acetate, fenchyl alcohol, p-methyldimethylbenzylcarbinol, methylphenylcarlbinyl acetate, methyl-n-valerate, muskmoskene, muscarone, methyl amyl ketone, phenylethyldimethylcarbinyl acetate, rose phenone, styrallyl propionate, tetra hydromuguol, tetra hydromuguyl acetate, tetrahydreolinalool acetate, verool, velveton, verdox, coniferan and yarayara, and a surface active agent which can be stably be dissolved in an aqueous solution of sodium hypochlorite."
Neither the South African nor the U.S. patents, however, indicate the advantages and usefulness of limiting the detergents either to (a) compounds having the generic structure: ##STR12## wherein at least one of R.sub.1 and R.sub.2 represents C.sub.10 -C.sub.12 straight chain or branched chain alkyl and when one of R.sub.1 or R.sub.2 is C.sub.10 -C.sub.12 branched or straight chain alkyl, the other or R.sub.1 or R.sub.12 is pH-adjusted hydrogen and wherein M.sub..alpha. and M.sub..beta. are the same or different and each represents alkali metal which may be sodium, lithium or potassium, or (b) to mixtures of compounds having the structure: ##STR13## with at least 2,4,4-trisubstituted tetrahydro pyranyl esters defined according to the structure: ##STR14## of excluding from the formulation a hydrotrope or of specifying the nature of the perfume oil useful in the perfumed bleach or sterilizing solution (wherein A and B are each separately methyl or taken together, complete a morpholino ring and wherein R.sub.3 " is straight chain alkyl having from 11 up to 13 carbon atoms).
U.S. Pat. No. 3,876,551 in attempting to solve the foregoing problem discloses a stable single phase aqueous alkali metal hypochlorite liquid perfume bleach or sterilizing composition comprising an aqueous mixture of (1) an amino oxide composition consisting essentially of at least one morpholino and/or dimethyl (C.sub.11 -C.sub.13 straight chain alkyl) amine oxide in an amount greater than 55% of said amine oxide composition, (2) at least one alkali metal hydroxide, (3) at least one alkali metal hypochlorite, and (4) a perfume oil compatible with the mixture capable of imparting a "woody" or a "floral" or a "clean fresh" or a "citrusy" note to the bleach or sterilizing composition; the mixture having a pH in the range of from 12 to 13.5 and the mixture excluding hydrotropes as well as all surfactants except the amine oxide. U.S. Pat. No. 3,876,551 also attempts to solve the foregoing problem by disclosing a process for producing the above-named mixture comprising the steps of combining an amine oxide composition consisting essentially of one or more morpholio and/or dimethyl C.sub.11 -C.sub.13 straight chain alkyl amine oxide(s) with the perfumed oil to form an amine oxide-perfume oil premix; admixing the amine oxide-perfume oil premix with an aqueous alkali metal hypochlorite solution, and combining an alkali metal hydroxide with the solution whereby the final pH of the mixture is from 12 up to 13.5. In a further effort to solve the foregoing problem U.S. Pat. No. 3,876,551 also discloses adjustment of the pH of the aqueous metal hypochlorite solution initially to the range of 12-13.5 and then combining the resulting aqueous hypochlorite solution with the aforementioned premix. The resulting composition is indicated to cause products to which said composition is applied to have eliminated there from the disagreeable characteristics "hypochlorite" aroma and instead to have a "clean fresh" or "floral" or "woody" or "citrusy" aroma to be imparted to the treated products. In addition, it is stated that the hands of the individual user after using and being in direct contact with the hypochlorite composition will not have the disagreeable characteristics "hypochlorite" aroma but instead will have a pleasant "clean fresh" or "floral" or "woody" or "citrusy" aroma.
The disadvantage of the system of U.S. Pat. No. 3,876,551 however, concerns (a) the inability to use a thickener in the system whereby the resulting liquid has a viscosity of 5-25 centipoises at 20.degree.-40.degree. C. and (b) the relatively low degree of chemical stability and substantive stability of the perfume oil and of the single liquid phase system. Nothing in U.S. Pat. No. 3,876,551 indicates such a high degree of stabilities of the perfume-hypochlorite system as exists in the system of the present invention; wherein there is also included a thickener. Indeed, the stabilities using the system of the instant invention are far greater even at levels as low as 3% hypochlorite and are also relatively stable (from a standpoint of chemical stability of perfume oil, substantive stability of perfume oil and phase separation stability taken in combination with one another) at levels of as high as 10% hypochlorite in aqueous solution. Thus, the instant system gives rise to unexpected, unobvious and advantageous properties over the systems taught in the prior art.
Furthermore, nothing in the prior art including the teaching of U.S. Pat. No. 3,876,551 states either explicitly or implicitly the compatability of a thickener in the instant system, such as sodium palmitate, sodium stearate, potassium palmitate, potassium stearate, lithium palmitate, lithium stearate, lithium laurate, potassium laurate or sodium laurate whereby a stable gel (as opposed to a liquid) phase perfumed hypochlorite system or perfumed oil stabilizer emulsifier system "premix" may be produced.
The combination of the compound group having the structure: ##STR15## (wherein R.sub.1, R.sub.2, M.sub..alpha. and M.sub..beta. are defined, supra) with perfume and hypochlorite bleach in general, is set forth in the Kao Soap Company, Japanese Pat. No. 25515/79 filed on Nov. 2, 1973 and opened for public inspection on June 19, 1975. Thus, on page 2, at column 4, line 15, the compound: ##STR16## is disclosed for use in conjunction with the perfumed hypochlorite bleaches. The claim of the Kao Soap Patent is as follows:
Furthermore, the use of such compounds as those having the structure: ##STR17## (wherein R.sub.1, R.sub.2, M.sub..alpha. and M.sub..beta. have been previously defined) with hypochlorite bleaches is documented in the brochure of Dow Chemical entitled "DOWFAX Surfactants" and is covered in the Dow Chemical Company U.S. Pat. No. 3,172,861 issued on Mar. 9, 1965.
Nothing in the prior art discloses, however, the utility of the thickeners of the instant application taken together with a perfume oil (e.g., at least one of the 2,4,4-trisubstituted tetrahydro pyranyl esters of our invention) and one of the compounds defined according to the generic structure: ##STR18## (wherein R.sub.1, R.sub.2, M.sub..alpha. and M.sub..beta. have been defined, supra) in hypochlorite bleaches, particularly where the hypochlorite concentration is greater than 7%. More particularly, nothing in the prior art discloses the use of such systems in conjunction with a thickener such as sodium palmitate, potassium palmitate, sodium stearate, potassium stearate, sodium laurate, potassium laurate, lithium laurate, lithium stearate orlithium palmitate, whereby a stable gelled perfumed hypochlorite mixture is formed or whereby a "premix" gel-hase perfume oil-stabilizing/emulsifying agent is formed.
The 2,4,4-trisubstituted tetrahydro pyranyl esters of our invention are unique insofar as the aforementioned systems are concerned for use in hypochlorite bleaches. Nothing in the prior art discloses any organic compounds even remotely similar to the 2,4,4-trisubstituted tetrahydro pyranyl esters of our invention for use as a stable aroma augmenting or enhancing agent in hypochlorite bleaches.